A Ni-0(eta(2)-(Si-H))(eta(2)-H-2) Complex That Mediates Facile H Atom Exchange between Two sigma-Ligands

作者：Connor Bridget A; Rittle Jonathan; VanderVelde David; Peters Jonas C^*

来源：Organometallics, 2016, 35(5): 686-690.

DOI：10.1021/acs.organomet.6b00985

sigma-adduct complexes of low-valent, late first-row metal complexes are highly unusual, and this is particularly true of d(10) systems. We have discovered a nickel/phosphine/silyl system that undergoes reaction with H-2 in solution to generate a species best described as Ni-0(C-2-(SiH))(eta(2)-H-2) on the basis of multinuclear NMR studies. Theoretical calculations suggest that the Ni center facilitates H atom exchange between the eta(2)-(SiH) and eta(2)-H-2 ligands via interconversion with a higher valent Ni-II isomer. This exchange is exploited in the selective, catalytic deuteration of exogenous silanes.

• 出版日期2016-3-14